JPH0539386A - Hydrogenated block copolymer composition excellent in oil resistance - Google Patents

Abstract

PURPOSE:To obtain the subject composition improved in flexibility, compression set, oil resistance, etc., by mixing a specified hydrogenated block copolymer with a rubber softener comprising a non-aromatic compound, a polyolefin hydrocarbon resin, and a polyphenylene ether resin. CONSTITUTION:100 pts.wt. hydrogenated block copolymer (A) having a number- average molecular weight of 5,000 to 1,000,000 and a molecular weight distribution of at most 10, obtained by hydrogenating a block copolymer consisting of 50-70wt.% polymer block composed mainly of at least two vinyl aromatic compounds and a polymer block composed mainly of at least one conjugated diene compound, is mixed with 50-500 pts.wt. rubber softener (B) comprising a non-aromatic compound, 100-250 pts.wt. polyolefin hydrocarbon resin (C) having an MFR of 0.1-50g/10min, and a polyphenylene ether resin (D) consisting of the bonding units of the formula [wherein R1 to R4 are each H, halogen or a (substituted)hydrocarbon group] and having a reduced viscosity (0.5dl/g chloroform solution at 30 deg.C) of 0.1 to 0.70 in an amount sufficient to provide a weight ratio of A to D of (90:10) to (30:70), thus giving the objective composition.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is excellent in flexibility, rubber elasticity (compression set) at high temperature, mechanical strength, and moldability, and is as thermoplastic elastomer as a chlorobrene rubber. The present invention also relates to a highly elastic hydrogenated block copolymer composition having excellent oil resistance, which has excellent oil resistance and can be used as a material for various molded products.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers, which are rubber-like soft materials and do not require a vulcanization process and have the same moldability as thermoplastic resins, have been used in automobile parts, home electric appliance parts, wire coatings, medical parts, It is useful in fields such as sundries and footwear. Among them, vinyl aromatic compound-conjugated diene compound block copolymer of a thermoplastic elastomer, for example, a block copolymer having a structure of polystyrene-polybutadiene-polystyrene is useful as a soft material excellent in processability. ， Because it is poor in heat resistance, weather resistance and oil resistance, its range of use was limited. The hydrogenated derivative of the vinyl aromatic compound-conjugated diene compound block copolymer (hereinafter abbreviated as hydrogenated block copolymer) of the thermoplastic elastomer improved with these drawbacks is recognized to have improved weather resistance and heat resistance. However, the oil resistance was the same as the conventional performance level.

Several proposals have been made regarding an elastomeric composition using the hydrogenated block copolymer.
For example, JP-A-50-14742 and JP-A-52-
65551 and JP-A-58-206644 disclose elastomeric compositions in which a hydrogenated block copolymer is mixed with a hydrocarbon oil and an olefin polymer, and JP-A-59-6236 is further disclosed. JP-A-59-131613 and JP-A-59-131613 disclose an elastomeric composition obtained by blending a hydrogenated block copolymer with a hydrocarbon oil, an olefin polymer and an inorganic filler in the presence of an organic peroxide and a cross-linking aid. Has been proposed to improve the rubber elasticity (compression set) of the resulting elastomeric composition at high temperature.

However, the elastomeric compositions of hydrogenated block copolymers obtained by these proposals are excellent in rubber elasticity but poor in oil resistance.

[0005]

The elastomeric composition of the hydrogenated block copolymer obtained by the above-mentioned proposal of the prior art has a rubber elasticity (compression set) when the oil resistance is improved.
When the rubber elasticity (compression set) is improved, the oil resistance becomes poor, and the directionality of the performance is determined by the compounding ingredients in the composition, and the oil resistance and rubber elasticity (compression set) performances are in conflict. It was a thing. Therefore, it is the current situation that an elastomeric composition of a hydrogenated block copolymer, which is excellent in both properties, cannot be obtained by the prior art, and it was taken for granted.

[0006]

The present invention has been made to solve the problems that were difficult with the conventional elastomer molding materials described above. In particular, the thermoplastic elastomer has processability and can be recycled. Elasticity at high temperature (compression set at 100 ° C)
It was made based on the demand for a molding material that has excellent oil resistance as good as that of chlorobrene rubber and that can satisfy the performance that has never been achieved. It has been found that the composition can be sufficiently achieved, and that it is a composition which is practically useful.

That is, the present invention provides (a) a block copolymer consisting of a polymer block A containing at least two vinyl aromatic compounds as a main component and a polymer block B containing at least one conjugated diene compound as a main component. Hydrogenated block copolymer obtained by hydrogenating polymer 100 parts by weight (b) Softener for non-aromatic rubber 150 to 500 parts by weight (c) Polyolefin hydrocarbon resin More than 100 parts by weight and 250 parts by weight Below (d) Bonding unit

[0008]

[Chemical 2]

(Wherein R ₁ , R ₂ R ₃ and R ₄ are each selected from the group consisting of hydrogen, halogen, a hydrocarbon group and a substituted hydrocarbon group) and a reduced viscosity (0. 5g / dl chloroform solution, measured at 30 ° C)
Is a homopolymer in the range of 0.15 to 0.70 and /
Alternatively, a polyphenylene ether resin which is a copolymer is composed of d, and the weight ratio of (a) to (d) is (a) / (d) =
Provided is a highly elastic hydrogenated block copolymer composition having excellent oil resistance of 90/10 to 30/70.

The present invention will be described in detail below. The hydrogenated block copolymer used as the component (a) in the present invention is a polymer block A mainly containing at least two vinyl aromatic compounds and a polymer block mainly containing at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer consisting of B and, for example, A
-BA, BABA, (AB) _4- Si, AB
A hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as -A-B-A.

The hydrogenated block copolymer contains a vinyl aromatic compound in an amount of 5 to 60% by weight, preferably 10 to 50% by weight. Further, referring to the block structure, a polymer block containing a vinyl aromatic compound as a main component. A represents a structure of a vinyl aromatic compound polymer block or a copolymer block of a vinyl aromatic compound containing more than 50% by weight, preferably 70% by weight or more of a vinyl aromatic compound and a hydrogenated conjugated diene compound. The polymer block B having a hydrogenated conjugated diene compound as a main component, and having a hydrogenated conjugated diene compound polymer block or a hydrogenated conjugated diene compound in an amount of more than 50% by weight. A copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound, preferably containing 70% by weight or more, It has the structure of a click.

Further, the polymer block A mainly composed of these vinyl aromatic compounds and the polymer block B mainly composed of the hydrogenated conjugated diene compound are hydrogenated in the molecular chains of the respective polymer blocks. Random distribution of conjugated diene compound or vinyl aromatic compound,
It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially block-like or any combination thereof, and the polymer block mainly containing the vinyl aromatic compound and the hydrogenation When there are two or more polymer blocks each containing the conjugated diene compound as a main component, the respective polymer blocks may have the same structure or different structures.

As the vinyl aromatic compound constituting the hydrogenated block copolymer, for example, one kind or two or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene and p-tert-butylstyrene, and among them, Styrene is preferred. Examples of the conjugated diene compound before hydrogenation that constitutes the hydrogenated conjugated diene compound include, for example, butadiene, isoprene, 1,3-pentadiene, and 2,3-
One kind or two or more kinds are selected from dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable. Then, the polymer block mainly composed of the conjugated diene compound before hydrogenation, the microstructure in the block can be arbitrarily selected,
For example, in the polybutadiene block, the 1,2-microstructure is 20-50%, preferably 25-45%.

The number average molecular weight of the hydrogenated block copolymer of the present invention having the above structure is 5,000 to 1.
000000, preferably 10,000 to 800,000,
More preferably, it is in the range of 30,000 to 500,000, and the molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)] is 10 or less.
Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

As a method for producing these block copolymers, any method may be used as long as it has the above-mentioned structure. For example, according to the method described in JP-B-40-23798,
As a method for producing a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer, and then synthesizing a vinyl aromatic compound-conjugated diene compound block copolymer in an inert solvent using a lithium catalyst or the like. Are, for example, Japanese Patent Publication No. 42-8704 and Japanese Patent Publication No. 43-6636.
Although it can also be obtained by the method described in Japanese Patent Publication No. JP-A-2003-242, hydrogenation synthesized by using a titanium-based hydrogenation catalyst that exhibits particularly excellent weather resistance and heat deterioration resistance of the hydrogenated block copolymer obtained. The block copolymer is most preferable, and hydrogenated in the presence of a titanium-based hydrogenation catalyst in an inert solvent, for example, by the method described in JP-A-59-133203 and JP-A-60-79005. Thus, the hydrogenated block copolymer used in the present invention can be synthesized.

At this time, at least 80% of the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is hydrogenated to form a polymer block mainly composed of the conjugated diene compound. Can be converted into an olefinic compound polymer block. Further, hydrogen of an aromatic double bond based on a vinyl aromatic compound copolymerized with a polymer block A mainly containing a vinyl aromatic compound and optionally a polymer block B mainly containing a conjugated diene compound. The addition rate is not particularly limited, but the hydrogen addition rate is preferably 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus or the like.

Next, the non-aromatic softening agent for rubber used as the component (b) in the present invention is an essential component for making the obtained composition a flexible rubber-like composition, and is a non-aromatic type. Mineral oils or liquid or low molecular weight synthetic softeners are suitable. Among them, mineral oil-based rubber softeners called process oils or extender oils, which are generally used for softening, increasing the volume and improving the processability of rubber, are a mixture of three aromatic rings, naphthene rings and paraffin chains. And the number of carbons in the paraffin chain is 5 out of all carbons.
Those that occupy 0% or more are called paraffin-based, and those with a naphthene ring carbon number of 30 to 45% are naphthene-based.
Those having an aromatic carbon number of more than 30% are considered aromatic.

The mineral oil-based rubber softening agent used as the component (b) of the present invention is preferably a naphthene-based or paraffin-based one in the above classification, and an aromatic-based one having an aromatic carbon number of 30% or more is However, it is not preferable in terms of dispersibility and solubility in the composition with the component (a). The properties of these non-aromatic softeners for rubber are kinematic viscosity at 37.8 ° C of 20 to 500 cst and pour point of -10 to -15 ° C.
And a flash point of 170 to 300 ° C. Although polybutene, low molecular weight polybutadiene, etc. can be used as the synthetic softening agent, the above-mentioned mineral oil-based rubber softening agent gives better results.

The blending amount of the softening agent as the component (b) is 150 to 500 parts by weight, preferably 150 to 400 parts by weight, relative to 100 parts by weight of the component (a). 500
If the content is more than about 1 part by weight, bleeding out of the softening agent is likely to occur, tackiness may occur in the final product, and mechanical properties may be deteriorated. When the amount is less than 150 parts by weight, the resulting composition becomes close to the resin composition,
In addition to tending to increase hardness and decrease flexibility, it is not preferable from the economical point of view.

Next, the polyolefin-based hydrocarbon resin used as the component (c) of the present invention is effective for improving oil resistance, processability, and / or heat resistance of the resulting composition. For example, polyethylene and isotactic Tic polypropylene or a copolymer of propylene and a small amount of other a-olefin, such as propylene-ethylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-
1-pentene copolymer, poly-4-methyl-1-pentene, polybutene-1 and the like can be mentioned. When using isotactic polypropylene or its copolymer as the polyolefin resin, MFR (ASTM
-D-1238-L condition, 230 ° C) is 0.1 to 50 g.
/ 10 minutes, especially 0.5 to 30 g / 10 minutes can be preferably used.

The blending amount of the component (c) is 100 parts of the component (a).
It is more than 100 parts by weight and 250 parts by weight or less, preferably 105 to 200 parts by weight, based on parts by weight. When the amount is more than 250 parts by weight, the resulting elastomeric composition is excellent in oil resistance, but the hardness of the resulting elastomer composition is too high, resulting in loss of flexibility, and it is not possible to obtain a rubber-like product. Rubber elasticity (compression set) is extremely deteriorated, which is not preferable.

Next, the polyphenylene ether resin used as the component (d) of the present invention is an essential component for improving the balance between the oil resistance and the compression set of the resulting composition, and the bonding unit.

[0023]

[Chemical 3]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each selected from the group consisting of hydrogen, halogen and hydrocarbon groups and may be the same or different from each other) Is a homopolymer and / or copolymer, and is 0.5 g
/ Dl chloroform solution having a reduced viscosity measured at 30 ° C in the range of 0.15 to 0.70 is used, and more preferably 0.20 to 0.60. As this polyphenylene ether resin, known ones can be used.

Specific examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6ethyl-1,4phenylene ether), poly (2,2).
6-diphenyl-1,4-phenylene ether), poly (2-methyl-6phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like. And also 2,6-dimethylpheno-
Also included are polyphenylene ether copolymers such as copolymers of phenol with other phenols (eg 2,3,6-trimethylphenol and 2-methyl-6-butylphenol).

Among them, poly (2,6-dimethyl-1,4)
-Phenylene) ether, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene) is further preferable. Ether is preferred. In the case of poly (2,6-dimethyl-1,4-phenylene ether), its reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is preferably in the range of 0.15 to 0.70, and more preferably in the range of 0.30 to 0.60.

The blending amount of the component (d) is preferably such that the weight ratio of the hydrogenated block copolymer of the component (a) to the polyphenylene ether of the component (d) is 90/10 to 30/70. You can choose to. When the weight ratio is less than 30/70, the elastomeric composition obtained has too high hardness, loses flexibility and becomes a resinous composition, and not only a rubber-like product cannot be obtained. However, rubber elasticity at high temperature [compression set (100 ° C. × 22 hours)] is inferior, which is not preferable. Further, in the case where the weight ratio exceeds 90/10, improvement of rubber elasticity (compression set) at high temperature as an effect of adding polyphenylene ether is not recognized, which is not preferable.

In addition to the above-mentioned components (a) to (d), the composition of the present invention may further contain an inorganic filler, if necessary. Inorganic fillers, which can be added as needed, not only have the advantage of reducing the product cost as an extender, but also have the advantage of imparting positive effects to quality improvement (oil resistance, compression set elongation). is there. Examples of the inorganic filler include calcium carbonate, carbon black, talc, clay, magnesium hydroxide, mica, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon) and titanium oxide. As channel black, channel black and furnace black can be used.

Of these inorganic fillers, talc, calcium carbonate and furnace black are economically advantageous and preferred. A conductive filler may be added to impart conductivity, and for example, conductive carbon such as Ketjen black may be used. The blending amount of the inorganic filler can be appropriately selected within the range of 1 to 300 parts by weight with respect to 100 parts by weight of the hydrogenated block copolymer of the component (a).

The hydrogenated block copolymer composition having excellent oil resistance of the present invention can be obtained by compounding the above-mentioned components, and if necessary, a flame retardant, glass fiber, carbon fiber. , An antioxidant, a heat resistance stabilizer, an ultraviolet absorber, a hindered amine light stabilizer, and a colorant can be added. As a method for compounding the hydrogenated block copolymer composition having excellent oil resistance of the present invention, a method used in the production of a usual resin composition or a rubber composition can be adopted, and a single-screw extruder, It can be compounded by using a melt kneader such as a shaft extruder, a Banbury mixer, a heating roll, a brabender, and various kneaders.

At this time, there is no limitation on the order of addition of each component. For example, all components are premixed by a mixer such as a Henschel mixer or a blender and melt-complexed by the above kneader, or any component is preliminarily mixed. An addition method such as mixing and master-batch melt-compositing, and further adding the remaining components to melt-composite can be adopted. The composite composition of the present invention can be molded by a commonly used thermoplastic resin molding machine, and can be used for injection molding, extrusion molding, blow molding.
Various molding methods such as molding and calendar molding can be applied.

[0032]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The test methods used for various evaluations in these Examples and Comparative Examples are as follows. (1) Hardness [−] JIS-K-6301, A type (2) Tensile strength [kg / cm ² ] and tensile elongation (%) JIS-K-6301, 2 mm thick injection sheet was used as a sample. The test piece used was a No. 3 dumbbell. (3) Oil resistance No. specified in JIS-K-6301. Using 3 test oils,
A test piece of 50 mm × 5 mm × 2 mm was immersed at 70 ° C. for 2 hours, and the weight change (%) before and after the immersion was determined. (4) Compression set [%] JIS-K-6301, 70 ° C and 100 ° C, 22 hours, 25% deformation.

The components blended are as follows. (1) <Component (a-1)> having a structure of hydrogenated polybutadiene-polystyrene-boron-added polybutadiene-polystyrene, bound styrene amount 31%, number average molecular weight 154000, molecular weight distribution 1.06, The amount of 1,2-bond of polybutadiene before hydrogenation is 28%, hydrogenation rate is 99%
The hydrogenated block copolymer (1) was synthesized using the Ti-based hydrogenation catalyst described in JP-A-60-79005 to obtain a component (a-1). <Component (a-2)> Polystyrene-has a structure of hydrogenated polybutadiene-polystyrene and has a bound styrene content of 33%, a number average molecular weight of 194000, and a molecular weight distribution of 1.
05, the amount of 1,2 bonds of polybutadiene before hydrogenation is 37
% And hydrogenation rate 99%, a hydrogenated block copolymer having a hydrogenation rate of 99%
It was synthesized using the Ti-based hydrogenation catalyst described in JP-A-133203 to give a component (a-2). <Component (a-3)> (polystyrene - hydrogenated polybutadiene) - ₄ has the structure of Si, bound styrene content of 26%, a number average molecular weight 384000, molecular weight distribution 1.4
6, 1,2 bond amount of polybutadiene before hydrogenation is 41%,
A hydrogenated block copolymer having a hydrogenation rate of 99% is disclosed in JP-A-59-1.
It was synthesized using the Ti-based hydrogenation catalyst described in JP-A-33203 to give component (a-3).

<Component (a-4)> Shell Chemical Company K
RATON-G1650 (2) Component (b) Diana Process Oil PS-32 manufactured by Idemitsu Kosan Co., Ltd. [paraffin-based process oil, kinematic viscosity: 31.42 cst
(40 ° C.), 5.42 cst (100 ° C.), average molecular weight 408, ring analysis; C _A = 0.1%, C _N = 32.8%,
C _P = 67.1%] (3) Component (c) Asahi Kasei polypropylene resin, E-1100 [MFR
(230 ° C.) 0.5 g / 10 minutes] (4) <Component (d-1)> As a polyphenylene ether resin, poly (2,6-dimethyl-1,4-phenylene) ether <reduced viscosity; 0.31 and 0.66> were synthesized and used as the component (d-1). <Component (d-2)> Polyphenylene ether resin containing 2,3,6-trimethylphenol in 5% 2,
A 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer (reduced viscosity 0.54) was synthesized from 6-dimethylphenol to obtain a component (d-2).

[0035]

Examples 1 to 4 Components (a-1), (a-2), (a-3) and (a-4) were used as hydrogenated block copolymers, and polyphenylene ethers had a reduced viscosity of 0.1. 6
Using the component (d-1) of 6 above, the components shown in Table 1 were mixed with a Henschel mixer, and then mixed with a twin-screw extruder having a diameter of 50 mm.
Melt kneading was carried out under the condition of 40 ° C. to obtain an elastomer pellet having a good surface texture. The pellets were evaluated as injection-molded products, and the results are shown in Table 1.

From these results, it is clear that the composition of the present invention has excellent oil resistance and rubber elasticity (compression set). Further, no stickiness was observed on the surface of the sample after the oil resistance test.

[0037]

[Table 1]

[0038]

Comparative Examples 1 to 4 As a hydrogenated block copolymer, (a-
1), (a-2) and (a-5), and (d-1) component having a reduced viscosity of 0.66 as polyphenylene ether. It was compounded in the same manner as in 4, and further molded and evaluated. The results are shown in Table 2.

From these results, it has been revealed that the compositions outside the scope of the present invention have excellent oil resistance and are inferior in rubber elasticity (compression set), and those excellent in rubber elasticity are inferior in oil resistance. (The samples of Comparative Examples 1, 2, and 3 after the oil resistance test had remarkable stickiness on the surface.)

[0040]

[Table 2]

[0041]

Example 5 As polyphenylene ether (d-2)
Formulated with the same composition as in Example 1 except that the components were used,
Melt kneading was performed under the same conditions, and injection molding was performed to obtain a test piece. When the physical properties were evaluated, hardness 85 and tensile strength 1
10 kg / cm ² , elongation 490%, oil resistance 12%, 70
A hydrogenated block copolymer excellent in oil resistance and rubber elasticity having characteristics of 38% compression set at 38 ° C. and 48% compression set at 100 ° C. was obtained.

When the tensile strength of this test piece was further measured at 100 ° C., it was found to be 80 kg / cm ² , exhibiting excellent heat resistance.

[0043]

Example 6 The component (a-
1) and (d-1) component having a reduced viscosity of 0.66 as polyphenylene ether, the components shown in Table 3 were mixed with a Henschel mixer, and the temperature was 250 ° C. in a twin screw extruder having a diameter of 50 mm. Melt kneading was carried out to obtain elastomeric pellets. Injection molding was performed using the pellets to obtain a test piece. The evaluation results are shown in Table 3.

[0044]

[Table 3]

[0045]

[Examples 7 and 8] High-density polyethylene (Suntech 1240: manufactured by Asahi Kasei Corporation) was used as the component (c) polyolefin-based resin, and the components shown in Table 4 were mixed in a Henschel mixer and mixed in a 50 mm diameter twin-screw extruder. Melted and kneaded at 250 ° C. to obtain elastomeric pellets having a good surface texture. The pellets were injection-molded to obtain test pieces, each evaluation was performed, and the results are shown in Table 4.

From these results, it was clarified that a composition having excellent oil resistance and rubber elasticity can be obtained even if high density polyethylene is used. No stickiness was observed on the surface of the sample after these oil resistance tests.

[0047]

[Table 4]

[0048]

The composition obtained according to the present invention is excellent in oil resistance, flexibility, heat resistance, mechanical strength, rubber elasticity at high temperature, as well as in chlorobrene rubber, and in molding processability and electric insulation. Since it is excellent, its fields of use have been conventionally desired to improve oil resistance, rubber elasticity and molding speed, molding yield, etc., automobile parts, home electric appliances parts, various wire coatings (insulation, sheaths) and various industrial parts. Can be suitably molded and used.

Specific applications include various gaskets, flexible tubes, hose coatings and the like.

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Claims (1)

[Claims] 1. (a) A polymer block A containing at least two vinyl aromatic compounds as a main component, and at least 1.
100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block B mainly containing conjugated diene compounds (b) a softening agent for non-aromatic rubber 1
50 to 500 parts by weight (c) Polyolefin hydrocarbon resin More than 100 parts by weight and 250 parts by weight or less (d) Bonding unit (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each selected from the group consisting of hydrogen, halogen, a hydrocarbon group and a substituted hydrocarbon group) and a reduced viscosity (0.
5 g / dl chloroform solution, 30 ° C, measurement) is 0.1
The polyphenylene ether resin, which is a homopolymer and / or a copolymer in the range of 5 to 0.70, has a weight ratio of (a) and (d) of (a) / (d) = 90/1.
It is 0 to 30/70. A highly elastic hydrogenated block copolymer composition having excellent oil resistance.